Pigment dyestuffs

ABSTRACT

DYESTUFFS OF THE FORMULA   1-(Y-NH-),4-(R-NH-),(Z)0-2,(Z)0-2-ANTHRAQUINONE   1-Y1,4-(R-NH-),6,9-DI(X-),(Z)0-2,(Z)0-2-ANTHRAQUINONE OR   1,4-DI(R-NH-),(Z)0-2,(Z)0-2-ANTHRAQUINONE   WHEREIN Z IS A SUBSTITUENT, ONE X IS A MEMBER NHR AND THE OTHER IS HYDROGEN OR A SUBSTANCE Z, Y IS AN OPTIONALLY SUBSTITUTED HYDROCARBON RESIDUE OR AN ACYL GROUP, Y1 IS HYDROGNE OR A SUBSTITUENT, AND R IS A MOIETY CO-B-CO-NH-E WHERE B IS A BOND, SATURATED OR IMSATIRATED ALKLENE WITH OR WITHOUT HETERO ATOMS AND SUBSTITUENTS, MONO OR POLYNUCLEAR ARYLENE WITH OR WITHOUT SUBSTITUENTS, CYCLOALKYLENE WITH OR WITHOUT SUBSTITUENTS OR HETEROARYLENE WITH OR WITHOUT SUBSTITUENTS AND E IS A RADICAL B OR AN ARALKYL GROUP; AS WELL AS THIER PREPARATION AND USE AS PIGMENTS; THE NOVEL DYESTUFFS ARE PIGMENT DYESTUFFS AND FREE OT SULFONIC ACID AND CARBOXYLIC ACID GROUPS.

United States Patent @tfic Jifiiiii 3,823,167 PIGMENT DYESTUFFSKarl-Heinz Peters, Cologne-Buchheim, and Riitger Neeff, Leverkusen,Germany, assignors to Bayer Aktiengesellschaft, Leverkusen, Germany NoDrawing. Original application June 25, 1969, Ser. No. 836,634, nowPatent No. 3,699,126. Divided and this application June 29, 1971, Ser.No. 158,066 Claims priority, application Germany, June 26, 1968, P 17 68745.5, P 17 68 755.7, P 17 68 756.8

Int. Cl. C09b 1/42 US. Cl. 260-372 2 Claims ABSTRACT OF THE DISCLOSUREDyestuffs of the formulae HN-R )ol )o-2 NHY X 0 NH-R I II I H-6m )o-2 uit 0 Y1 (In (I) PTHR (Z)o UfiQM-z H Y 0 NHR (III) wherein Z is asubstituent. one X is a member NHR and the other is hydrogen or asubstituent Z, Y is an optionally substituted hydrocarbon residue or anacyl group, Y, is hydrogen or a substituent, and R is a moiety COBCONH-E where B is a bond, saturated or unsaturated alkylene with orwithout hetero atoms and substituents, mono or polynuclear arylene withor without substituents, cycloalkylene with or without substituents orheteroarylene with or without substituents and E is a radical B or anaralkyl group; as well as their preparation and use as pigments; thenovel dyestuffs are pigment dyestuffs and free of sulfonic acid andcarboxylic acid groups.

This application is a division of copending application, Ser. No.836,634, filed June 25, 1969, now US. Pat. 3,699,126.

The dyestulfs according to this invention comprise anthraquinones with anovel moiety NHR which is further defined as CO--B--CONHE. Preferredgroups of dyestuffs of the general formulae (I), (H), and (III) arethose which are free of sulfonic acid and carboxylic acid groups. In thenovel moiety R, i.e. CO-BCONHE, B is preferably an arylene radicalespecially a phenylene radical which may contain substituents such asthose listed below. E is an alkyl, a heteroaryl or an aryl radicalespecially phenyl which may contain the below listed substituents.

The subject matter of the present invention comprises dyestuffs of theformula wherein Z is a substituent preferably selected from the groupcomprising hydrogen; halogen such as chlorine, fluorine or bromine;alkyl, preferably C C alkyl; nitro; amino; hydroxy; cyano; carboxy;alkoxy, preferably containing 1 to 3 carbon atoms; aryloxy, preferablyphenyloxy, C alkyl mercapto, aryl mercapto such as phenyl mercapto;aryl, especially phenyl or naphthyl; C alkyl carbonyl amino such asacetyl amino, valeryl amino and stearoyl amino; aryl carbonyl amino suchas naphthoyl and benzoyl amino; aryl sulfonyl amino, such as benzenesulfamide and C alkyl sulfonyl amino; carbamoyl; aryl sulfonyl such asphenyl sulfonyl; C alkyl sulfonyl; carboXy alkyl esters wherein thealkyl members contain 1 to 5 carbon atoms; carboxy aryl estersespecially phenyl esters; sulfonic acid aryl esters, such as sulfonicacid phenyl esters; sulfonic acid alkyl esters with l-6 carbon atoms;carbalkoxy with 1-5 carbon atoms; carbaryloxy especially naphthyl orphenyl carbonyl; arylamino especially anilino; alkylamino with 1 to 17carbon atoms; alkenylamino with 1 to 17 carbon atoms; cycloalkylamino,preferably cyclohexyl amino; aralkylamino especially benzyl or phenylethyl amino; wherein the above-mentioned cyclic radicals can contain 0to 4 substituents per ring selected from the group consisting ofchlorine, fluorine, bromine, nitro, hydroxy, alkoxy, with 1 to 6carbons, trihaloalkyl with 1-6 carbon atoms such as trifluoromethyl;alkyl carbonylamino with 1-6 carbon atoms such as acetyl amino, alkylcontaining 1 to 6 carbon atoms, sulfamoyl and cyano; X stands for amember Z or NHR wherein when one X is NHR, the others are Z; R standsfor the grouping -CO--B-CONHE wherein B is selected from the groupconsisting of a single bond; saturated alkylene with 1 to 17 carbonatoms which can contain in the alkylene chain hetero atoms selected fromthe group consisting of O, S and NH and further including the memberssubstituted alkylene and hetero-substituted alkylene chains wherein thesubstituents may be selected from the group consisting of hydroxy, alkylcarbonyl amino with 1-6 carbons such as acetyl amino alkoxy with 1-6carbon atoms and carboxy; unsaturated alkylene with 1 to 17 carbon atomswhich may contain the same hetero atoms and substituents mentioned forthe saturated alkylene chain; mono-nuclear arylene preferably phenylene;polynuclear arylenes such as naphthylene, biphenylene, azo benzene,azoxybenzene, hydrazobenzene, benzophenone, azo biphenyl, diphenylmethane, diphenyl ether, terphenyl, biphenyl azo biphenyl; cycloalkylenesuch as cyclohexyl, cyclopentyl and bicycloheptene; hetero arylenecontaining 5 or 6 members which may contain hetero members selected fromthe group consisting of oxygen, sulfur, and nitrogen, especiallyfuranyl, thiophenyl and pyridinyl wherein the above cyclic members cancontain 0-4 substituents per ring, selected from the group consisting ofhalogen such as chlorine, fluorine and bromine, alkyl with 1-6 carbonatoms, hydroxy, alkoxy with 1 to 6 carbon atoms, alkyl carbonyl amino,such as acetyl amino, nitro. The member E is selected from the groupconsisting of saturated alkyl with 1 to 18 carbon atoms which maycontain hetero atoms selected from the group consisting of O, S and NHfurther including the members substituted saturated C alkyl with orwithout hetero atoms with substituents selected from the groupconsisting of hydroxy, alkoxy with 1 to 6 carbon atoms, carboxy, andalkyl carbonyl amino with 1-6 carbons such as acetyl amino; unsaturatedalkyl with 1 to 18 carbon atoms which may contain hetero atoms and/orsubstituents as defined for the saturated alkyl members; cyclo alkylwith up to 9 carbon atoms, especialy cyclohexyl and cycloalkyl which mayfurther contain 1 or more hetero atoms selected from the groupconsisting of nitrogen, oxygen, and sulfur, especially sulfurcyclopentyl S, S dioxide; aralkyl, preferably benzyl but includingphenyl ethyl and including hexahydrobenzyl; mono or polycycloaryl suchas phenyl, naphthyl, anthracenyl, pyrenyl, diphenyl,tetrahydronaphthylene, chrysene and preferably phenyl; hetero arylmembers contain preferably 0, S, or N hetero atoms especiallybenzofuranyl, pyridinyl, carbazolyl, pyrimidinyl, triazolyl,benzotriazolyl, thiazolyl, benzothiazolyl, piperazinyl, furanyl andthiophenyl; or cycloalkylene sulfones with up to 9 members per ring;where the cyclic members listed above can contain -4 substituents perring selected from the group consisting of halogen such as chlorine,bromine, fluorine, nitro, alkyl with 1 to 12 carbon atoms, hydroxy alkylwith 1 to 12 carbon atoms, cyclo alkyl such as cyclohexyl, trihalo alkylsuch as trifluoromethyl, hydroxy, alkoxy with 1 to 3 carbon atoms,aryloxy such as phenoxy, carboxy alkyl carbonylarnino such asacetylamino, cyano, arylamino especially phenylamino which may containfurther substituents such as methyl and methoxy, alkyl sulfonyl with 1to 6 carbon atoms, aryl sulfonyl such as phenyl sulfonyl, alkyl carbonylwith 1 to 6 carbon atoms, aryl carbonyl such as phenyl carbonyl, carboxyalkyl esters with 1 to 6 carbon atoms, sulfamoyl, which can contain asN-substituents tolyl, hydroxy alkyl with 1 to 6 carbons such as hydroxyethyl or phenyl radicals; alkyl or aryl sulfonyl amino especially phenylor methyl sulfonyl amino; carbonamide, phenyl azo or phenyl azoxy whichmay contain carbonamide substituents.

One preferred class of dyestuffs of formula (I) is in which Y denotes Calkyl carbonyl, aryl carbonyl, aryl sulfonyl; C alkyl sulfonyl, aryl Calkyl, C al'kenyl, cycloalkyl, aralkyl wherein the aryl radicals cancontain 0-4 substituents per ring selected from the group consisting ofCl, F, Br, N0 OH, CF COCH CN, SO NH alkyl with l to 6 carbon atoms andalkoxy with 1 to 6 carbon atoms.

Another preferred class is 4 Still another preferred class is o IIIHR(Zlo-z C b i D (2)0-2 I 0 NHR The compounds according to this inventionare prepared according to known processes, for example, by acylatinganthraquinone derivatives of the formula i R )o2 C i D (ZN-2 X: 1 z I)in which one of the X s can be an amino and the others are selected fromthe definitions given above for X and Z is as defined above. Thesecompounds (11) are reacted with reactive derivatives, preferably thehalides, anhydrides or alkyl esters of dicarboxylic acid of the generalformula COOHBCOOH in which B is defined as above with at least one moleof the said reactive derivatives being used for every free amino groupin (II) and by subsequent reaction with an amine of the general formulaNHgE in which E is as defined above by using at least one mole of theamine for every group 'NH of '(II) which is to be converted into aradical NI-I'R. Since the first preferred group of dyestuffs of thisinvention are those containing two radicals NHR the preparationaccording to this first process involves two moles of acid and two molesof amine for each mole of anthraquinone (II) utilized. In anotherpreferred process a single NHR radical is desired, thereby requiringonly one mole of acid and amine.

The compounds can also be prepared by known methods involving theacylation of anthraquinone derivatives of the formula (II) with at leastone mole per free NH group of a reactive derivative of an N-substituteddicarboxylic acid monoamide of the formula in which B and E are definedas above. Suitable reactive derivatives are especially the halides andalkyl esters.

More specifically, the compounds according to the invention can bepreferably prepared, for example, by reacting an amine of the formula(II) with an excess of a dicarboxylic acid halide of the formula inwhich B is defined as above and A is fluorine, chlorine, or bromine, ata temperature between 40 and 220 C. in an organic solvent such asbenzene, toluene, xylene, chlorobenzene, dichlorobenzene,trichlorobenzene, nitrobenzene, and optionally in the presence of basiccatalysts such as pyridine, piperidine, morpholine, trimethylamine,collidine, picoline, lutidine, quinoline, with or without the additionof acid binding agents such as sodium carbonate, potassium carbonate,sodium or potassium bicarbonate or quick lime until the starting amineis completely converted and subsequently reacting the resulting compoundof the formula If: (I? ITIH-CO-B-OO-A (Z )0- C I D Z )o-:

| X; 0 X3 (III) in which B is an defined above, and one of theadditional substituent X can be a radical NHCOBCOA with the others beingas defined above for X after separation from the reaction solution orwithout isolation with an excess of an amine of the formula NH E attemperatures between 40 and 220 C. with the use of the amine as solventor the use of an organic solvent such as benzene, toluene, xylene,chlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene,optionally in the presence of basic catalysts such as pyridine,piperidine, morpholine, trimethylamine, collidine, picoline, 'lutidine,quinoline, with or without the addition of acid binding agents such assodium carbonate, potassium carbonate, sodium or potassium bicarbonateor quick lime.

Examples of amino atnhraquinones (II) preferably used for thepreparation of the compounds (I) according to the invention are:

4-amino-1-methylamino anthraquinone, 4-amino-l-hexahydroanilinoanthraquinone, 4-amino-l-acetylamino anthraquinone,4-arnino-l-chloroacetylamino anthraquinone, 4-amino-1-butylaminoanthraquinone, 4-amino-l-stearoylamino anthraquinone,4-amino-l-benzylamino anthraquinone, 4-amino-1-(2,3- or4-chlorobenzoylamino)- anthraquinone, 4-amin0-1-(2,4- or2,5-dichlorobenzoylamino)- anthraquinone, 4-amino-1-(2,3- or4-nitrobenzoylamino)- anthraquinone, 4-amino- 1-(4-ehloro-3-nitrobenzoylamino anthraquinone, 4-amino- 1- 3 ,5-dinitrobenzoylamino) -anthraquinone, 4-amino-l-(3- or4-trifluorornethylbenzoylamino)- anthraquinone, 4-aminol-(4-methylbenzoylamino -anthraquinone,4-amino-l-(4-methoxybenzoylamino)-anthraquinone,4-amino-1-(3-sulfamoylbenzoylamino) anthraquinone,4-amino-3-methyl-l-(4-chlorobenzoylamino)- anthraquinone,4-amino-5-nitro-l-benzoylamino-anthraquinone, 4-amino-3-bromo-1-(paratoluenesulfamido)- anthraquinone, 4-amino-1-anilino anthraquinone,4-aminol- (4-methoxyanilino anthraquinone, 4-amino-3-bromol-(4-methylanilino) -anthraquinone,4-amino-3-bromo-1-(2,6diethyl-4-methylanilino)- anthraquinone,4-amin0-1-(2- or 4-bromobenzoylamino)- anthraquinone,l,4-diamino-anthraquinone, 2-brorno-1,4-diamino-anthraquinone,2,3-dich1orml,4-diamino-anthraquinone,5,8-dichloro-l,4-diamino-anthraquinone,2-nitro-l,4-diamino-anthraquinone, S-nitro-1,4-diamino-anthraquinone,2-bromo-5-nitro-1,4-diamino-anthraquinone, 5 -benzoylaminol,4-diamino-anthraquinone, S-acetylarnino-l,4-diarnino-anthraquinone,1,4-diamino-S,8-dihydroxy-anthraquinone,1,4-diamino-Z-phenoxy-anthraquinone,1,4-diamino-2,3-diphenoxy-anthraquinone,1,4-diamino-5,8-dihydroxy-2-phenylmercaptoanthraquinone,6-bromo-l,4-diamino-S,8-dihydroxy-2-phenylmercapto-anthraquinone,1,4-diamino-2-phenylsulphonyl-anthraquinone,5-nitro-1,4-diamino-2-(4-chloro-phenylsulphonyl)- anthraquinone,1,4-diamino-anthraquinone-2-sulphonic acid-phenyl ester,1,4-diamino-2-(4-methoxy-phenyl) -3 -cyanoanthraquinone,1,4-diamino-anthraquinone-3'-carboxylic acid amide,

ethyl ester, and butyl ester.

Further examples of amino-anthraquinone of the formula (II) preferablyused for the preparation of the compounds according to the inventionare:

1,5- and 1,8-diamino-anthraquinone,

1,4,5 ,8-tetramino-anthraquinone,

4-chloro-1,5-diarnino-anthraquinone,

2,4,6,8,tetrabromo- 1,5 -diamino-anthraquinone,

3-chloro-4,8-diamino-1,S-bis-(4-methyl-anilino)- anthraquinone,

4,5 -diamino- 1 -benzoylamino-anthraquinone,

4,8-diaminol-hydroxy-anthraquinone,

4,8-diamino-1,5-dihydroxy-anthraquinone,

4,5 -diaminol ,8-dihydroxy-anthraquinone,

4,5 ,8-triaminol-hydroxy-anthraquinone,

4,8-diamino-1,5-dimethoxy-anthraquinone,

2,6-dibromo-1,5-diamino-4,8-dihydroxyanthraquinone;

the mixture obtained when 4,8-diamino-1,5-dihydroxyor4,5-diamino-1,8-dihydroxy-anthraquinone is brominated e.g. in sulphuricacid and which contains about one bromine atom per mole of4,8-diamino-1,5-dihydroxyor 4,5-diamino-1,8-

dihydroxy-anthraquinone, 3-bromo-1,4,8-triamino-S-hydroxy-anthraquinone,2-bromo-4,5,8-triamino-l-hydroxy-anthraquinone, or2-(4,-methoxyphenyl)-1,5-diamino-4,8-dihydroxyanthraquinone.

The reactive derivatives of the dicarboxylic acids preferably includethe halides especially the fluorides, chlorides, and bromines as well asthe esters and anhydrides, particularly the alkyl esters and especiallythe methyl or ethyl esters. Aliphatic dicarboxylic acids may be usedsuch as oxalic, malonic, succinic, glutaric, adipic suberic 'azelaic,sebacic; aliphatic dicarboxylic acids containing hetero atoms such asdiglycolic acid, thio diglycolic acid, methylene-bis-thioglycolic acid,di-thio-diglycolic acid, imino-diacetic acid; substituted aliphaticdicarboxylic acids such as, heptadecane-dicarboxylic acid- (1,8) or-(1,9), hydroxy-succinic acid, acetone-dicarboxylic acid,acetylarnino-succinic acid, Z-acetylaminoglutaric acid; cycloaliphaticdicarboxylic acids, such as cyclohexane-dicarboxylic acid-(1,2) or-(1,4), campheric acid; bicyclic dicarboxylic acids, such asbicyclo[2,2,1]- heptene-(5)-dicarboxylic acid-(2,3); unsaturateddicarboxylic acids, such as fumaric acid, 1,2,3,6-tetrahydrophthalicacid; mononuclear arylene-dicarboxylic acids, such asbenzene-dicarboxylic acid-(1,2), -(1,3) or -(1,4), 4-chloro-isophthalicacid, S-nitro-isophthalic acid, 2-chloro-terephthalic acid,Z-nitro-terephthalic acid, 2,5-dichloro-terephthalic acid,4-hydroxy-isophthalic acid, 2,5-dimethoxy-terephthalic acid,2,5-difiuoro-terephthalic acid, tetrachloro or tetrafluoro-terephthalicacid; polynuclear condensed arylene-dicarboxylic acids, such asnaphthalenedicarboxylic acid-(1,4)-, -(l,5) or -(2,6); polynuclearannellated arylene-dicarboxylic acids, such as diphenyl-dicarboxylicaccid-(4,4), diphenyl-sulphone-dicarboxylic acid- (4,4'azobenzene-dicarboxylic acid- (4,4' azoxybenzene-dicarboxylicacid-(4,4'), hydrazobenzene-dicar-boxylic acid-(4,4'),benzophenone-dicarboxylic acid-(2,4), diphenylether-dicarboxylicacid-(4,4' diphenylmethane-dicarboxylic acid-(4,4),p-terphenyl-dicarboxylic acid-(1,4),4'-carboxy-biphenyl-4azo-4-biphenyl-carboxylic acid-(4'), orhetero-arylene-dicarboxylic acids such as 2,5-furandicarboxylic acid,2,S-thiophene-dicarboxylic acid, pyridine-dicarboxylic acid-(2,3),-(2,4),

Example of amines of the formula NH E serving for the preparation of thecompounds used according to the invention are:

aliphatic amines such as methylamine, ethylamine, propylamine, n-,isoand tert.-butylamine, dodecyl-, tetradecylor hexadecylamine,9-amino-heptadecane, stearylamine; substituted aliphatic amines, such asZ-aminoor l-amino-ethanol, 3-amino-propanol, amino-acetic acid,G-amino-hexanic acid; amino-alkanes with chain-positioned hetero atom,such as 2-(2-amino-ethyl-amino)- ethanol (1), 3 methoxypropylamine, 3ethoxy-propylamine, 3 butyloxy propylamine, 3-(2-ethyl-hexyloxy)-propylamine, 2-amino-diethyl sulphide; alkenyl-amines, such asallylamine; cycloalkyl-amines, such as cyclohexylamine,2-(Z-hydroxy-ethyl)-cyclohexylamine, 2-, 3- or 4 methyl-cyclohexylamine,hexahydro-benzylamine; cycloalkyl-amines with interrupting hetero atomsin the alkylene chain, such as 3-amino-sulpholane,N-(Z-aminoethyl)-piperazine; aralkyl-amines, such as benzylamine,l-amino-lor -2-phenyl-ethane, w-amino-acetophenone; optionallysubstituted aryl-amines with optionally annellated or condensed arylnuclei, such as aniline, 2-, 3- or 4-chloro-aniline, 2,3-, 2,4-, 2,5-,3,4- or 3,5-dichloroaniline, 2,4,5-trichloroaniline, 2-, 3- or4-nitroaniline, 4- chloro-2-nitro-aniline, 5-chloro-2-nitro-aniline,3-chlor0- 4 nitro aniline, 2,5-dichloro-4-nitro-aniline,2,4-dinitroaniline, 6 -bromo- 2,4-dinitro-aniline, 2-, 3- or4-aminotoluene, 2-, 3- or 4-amino-benzotrifiuoride, 4-chloro-2-amino-toluene, 5-chloro-2-amino-benzotribuoride,4,5-dichloro-2-amino-toluene, 4-, 5- or 6-nitro-2-amino-toluene,4-chloro-3-amino-toluene or -benzo-trifluoride, 2-ethylaniline,xylidines, S-amino-l,3-bistrifiuoromethyl-benzene, 2amino-1,3,5-trimethyl-benzene, 4-amino-1-methyl-3,5- diethyl-benzene,4-amino-l,3-dimethyl-S-ethylbenzene, 4- dodecyl-aniline,5,6,7,S-tetrahydro-naphthylamine-( 1), or -(2),4-amino-l-cyclohexylbenzene, 1- or 2-amino-naphthalene,Z-amino-anthracene, l-amino-pyrene, 6-aminochrysene, 2- or4-amino-diphenylamine, 4-amino-4'-methyl-diphenylamine,3-amino-4-methyl-diphenylamine, 2-, 3- or 4-arnino-diphenyl ether, 2-,3- or 4-amino-1-methoxybenzene,4-chloro-5-nitr0-2-amino-l-methoxy-benzene, 4'- amino 4methoxy-diphenylamine, (2-hydroxyethyl)-('4- amino pheny'l) sulphone,methyl (4-amino-phenyl)- sulphone, 4 amino 3-methoxy-diphenyl-amine,4-amino- 1,3 dimethoxy benzene, 6-chloro-4-amino-1,3-dimethoxy-benzene,2-amino-1,4-diethoxy-benzene, 3-amino-4- methoxy diphenylsulphone, 4amino acetophenone, 4- amino-benzophenone, 2-, 3- or 4-amino-benzamide,4- amino-benzoic acid-methyl or -ethyl ester, 3-nitro-4-amino-benzamide, 4 chloro 2 amino-benzonitrile, 4- amino-isophthalicacid dintrile, 4-amino-isophthalic acid diamide, 6-amino-naphthoic acidamide(2), 3- or 4-aminobenzene-sulphonic acid amide,3-amino-benzene-sulphonic acid-(Z-hydroxycthyD-amide,4-amino-benzene-sulphonic acid anilide, 2-amino-benzoic acid-sulphonicacid-(4)-diamide, 4-amino-azobenzene,4-amino-azobenzene-carbonamide-(4'); or hetero-aromatic amines such as3- or 2- amino-dibenzofuran, 2-amino-pyridine, Z-aminomethylpyridine, 3ethyl 3-amino-carbazole, 2-amino-4-methylpyrimidine, 3 amino 1,2,4triazole, S-amino-Z-phenylbenzotriazole, Z-amino-thiazole,2-amino-benzo-thiazole, 6-amino-2-methyl-benzothiazole, or6-methoxy-2-aminobenzothiazole.

The dyestuffs so prepared are obtained in a form suitable for pigments,or they can be brought into a fine division by a known after-treatment,in order to be converted into a form suitable for pigments, for example,by dissolving or swelling them in strong inorganic acids such assulphuric acid and pouring the mixture on to ice. The fine division canalso be achieved by grinding with or without grinding auxiliaries, suchas inorganic salts or sand, optionally in the presence of solvents suchas toluene, xylene, dichlorobenzene or'N-methyl-pyrrolidone. Thestrength of colour and the transparency of the pigments can beinfluenced by varying the after-treatment.

The pigments used according to the invention can be used for theproduction of very fast pigmented systems, such as mixtures wtih othersubstances, preparations, coating agents, printing colours, colouredpaper and coloured macro-molecular materials. The term mixture withother substances comprises, for example, mixtures with inorganic whitepigments such as titanium dioxide (rutile) or with cement. Preparationsare, for example, flush pastes with organic liquids, or pastes and finepastes with water, dispersing agents and possibly preservatives. Theterm coating agent stands, for example, for physically or oxidativelydrying lacquers, stoving lacquers, reaction lacquers, two-componentlacquers, disperse by dyestulfs for weather-fast coatings and sizecolours. The printing colours comprise those for paper, textile andmetal sheet printing. The macromolecular substances can be of naturalorigin, such as caoutchour, or they can be obtained by chemicalmodification, such as acetyl cellulose, cellulose butyrate or viscose,or they can be synthetically produced, such as polymers, polyadditionproducts and polycondensates. Examples are plastic masses such aspolyvinyl chloride, polyvinyl acetate, polyvinyl propionate;polyolefines, e.g. polyethylene or polypropylene; polyesters, e.g.polyethylene terephthalate; polyamides, superpolyamides, polymers andcopolymers from acrylic esters, methacrylic esters, acrylonitrile,acrylamide, butadiene, styrene; as well as polyurethanes andpolycarbonates. The substances pigmented with the claimed products maybe present in any form.

The compounds used according to the invention have excellent pigmentproperties and are not only eminently fast to Wet processing, oil, acid,lime, alkali, solvent, overcoating, overspraying, sublimation and stableto heat and vulcanisation, but they also give very good yields, they caneasily be dispersed in plastic materials and have outstanding fastnessto light and Weather.

The parts given in the Examples are parts by weight.

EXAMPLE 1 (a) 8 parts4-(4-chloro-benzoylamino)-1-[4-(3-chlorophenylcarbamoyl)benzoylamino]anthraquinone which have been finely divided by grinding in a vibratormill with 2 parts xylene and 160 parts sodium chloride and washing outthe sodium chloride, are ground with a stoving lacquer obtained from 25parts coconut oil alkyd resin (40% coco nut oil), 10 parts melamineresin, 50 parts toluene and 7 parts glycol monomethyl ether in anautomatic Hoover- Muller grinding machine. The mixture is applied to thesubstrate to be coated, the lacquer is cured by stoving at C., and thereare obtained violet lacquer coats of good covering power and of verygood fastncss to overcoating and outstanding fastness to light andweather.

(a-I) Pigmented stoving lacquers of similar fastness properties areobtained by using 15-25 parts of the above alkyd resin or of an alkydresin based on cotton seed oil, dehydrated castor oil, castor oil orsynthetic fatty acids and replacing the above amount of melamine resinwith 10-15 parts of the aforesaid melamine resin or of a condensationproduct obtained from formaldehyde with urea or benzoguanamine.Pigmented stoving lacquers of similar good fastness properties and asimilar shade are obtained by replacing the above4-(4-chloro-benzoylamino)-1-[4- (3chloro-phenylcarbamoyl)-benzoylamino]-anthraquinone wtih correspondingamounts of finely divided 4- (4-chloro-benzoylamino) -1- [4-(4-methyl-phenylcarbamoyl) -benzoylamino] -anthraquinone,

4-(4-chloro-benzoylamino -1- [4- (2,3-dichloro-phenylcarbamoyl -benzoylamino] -anthr aquinone,

4-benzoylamino-1- [4-(2,3-dichloro-phenylcarbamoyl benzoylamino-anthraquinone,

4 benzoylamin o-1- [4-(2,5dichloro-phenylcarbamoyl) benzoylamino]-anthraquinone, or

4-benzoylamino-1- [4- (4-nitro-phenylcarbamoyl -benzoylamino]-anthraquinone.

(a-II) Violet shades also occur by use of the following compounds:

1,4-di- [4- (2, -dichloro-pheny1-carbamoyl -benzoylamino]-anthraquinone,

l,4-di- [4- 2-chloro-5-methyl-ph enyl-carbamoyl -benzoylamino]-anthraquino ne,

1,4-di- [4- (2,4,6-trimethyl-phenyl-carbamoyl) -benzoylamino]-anthraquinone,

5 ,1,4-di-[4-(n-butyl-carbamoyl) -b enzoylamino] -anthraquinone,

S-nitrol,4-di- [4- (n-dodecyl-carbamoyl) -benzoylamino] anthra quinone,

S-nitro-1,4-di-[4-(2-ch1orophenyl-carbamoyl)-benzoy1- amino]-anthraquinone, or

5-nitro-1,4-di- [4- 4-methyl-phenyl-carb amoyl) -benzoyl] anthraquinone.

(a-III) The following compounds give blue lacquers:

1,5-dihydroxy-4, 8-di- 4-phenyl-carbamoyl-benzoylamino) -anthraquinone,

1,5-dihydroxy-4, 8-di- (4-methyl-carbamoyl-benzoylamino) -anthraquinone,

1,5-dihydroxy-4, S-di- (n-butyl-carbamoyl-benzoylamino) anthraquinone,

1, S-dihyd roxy-4, 5-di- 4-phenyl-carbamoyl-benzoylamino -anthraquinone,

1, 8 -dihydroxy-4,5 -di- (4-methyl-carbamoyl-b enzoyl anthraquinone,

1, 5-dihydroxy-4, 8-di- [4- 2-chloro-pheny1-carbamoyl) benzoylamino]-anthraquinone, or 1 ,5 -dihydroxy-4,8-di-(n-dodecyl-carbamoyl-benzoylamino) -anthraquinone.

(b) If, instead of the amount of pigment stated above, 1 to 10 parts ofa mixture of titanium dioxide (rutile type) with one of the pigmentsstated in Example 1(a) are incorporated with the lacquer stated inExample 1(a) in a ratio of 05-50: 1, then the same method of working upyields lacquer coats of the same fastness properties and a violet orblue shade shiftin to white as the content of titanium dioxideincreases.

(c) The 4-(4-chloro-benzoylamino) 1 [4 (3-chlorophenylcarbamoyl)benzoylamino] anthraquinone described in Example 1(a-I) is prepared byheating 20 parts 4-amino-1-(4 chloro-benzoylamino)-anthraquinone with 20parts terephthalic' acid dichloride in 400 parts nitrobenzene at 90110C. until the starting amine can no longer be detected. The4-(4-chloro-benzoylamino)-1-(4- chloroformyl-benzoylamino)-anthraquinonepresent in the form of red needles is isolatedand 10 parts thereof areheated in the presence of 3 parts of N,N-dimethyl-aniline and 4 parts3-chloro-aniline in 200 parts nitrobenzene at 120-145 C. until the acidchloride is completely converted. The product is filtered off withsuction at 100 C., washed with warm-nitrobenzene, dimethyl formamide,methanol and hot Water, and the dyestuff present in the form of violetneedles is dried at 50 C. in a circulating air cabinet. The samecompound is obtained, when the nitrobenzene is replaced with1,2-dichlorobenzene and the N,N-dimethyl-aniline is replaced withequivalent amounts of sodium carbonate, potassium carbonate or pyridine.

The other compounds stated in Example 1(a-I) are obtained when the4-amino-1-(4-chloro-benzoylamino)- anthraquinone is replaced withequivalent amounts of 4- amino-1benzoylamino-anthraquinone or the3-chloroaniline is replaced with equivalent amounts of 2,3- or2,5-dichloroaniline or 4-nitro-aniline, or when 1-(4-chloro-benzoyl-amino) 4 (4 chloroformyl-benzoylamino)-anthraquinone isreacted in p-toluidine as solvent and reaction partner at 140-160 C. Theother dyestuffs described in the following Examples are obtained in ananalogous manner.

The 1,4-di-[4-(2,5-dichloro-phenylcarbamoyl)-benzoylaminol-anthraquinonedescribed in Example 1(aII) is prepared, for example, by introducing 20parts l,4-diamino-anthraquinone at C. with stirring into a solution ofparts terephthalic acid dichloride in 250 parts of aniline-freeanhydrous nitrobenzene and stirring at -1 10 C. until the1,4-diamino-anthraquinone is completely acylated. The mixture is allowedto cool, the precipitated 1,4-di-(4chloroformyl-benzoylamino)-anthraquinone which is present in the form ofyellowish red prisms is filtered otf with suction, the excess ofterephthalic acid dichloride is washed out with anhydrous nitro benzene,and the nitrobenzene-moist filter cake is reacted, after dilution with560 parts of aniline-free anhydrous nitrobenzene, with 39 parts2,5-dichloro-aniline in the presence of 20 parts N,N-dimethyl-aniline at-120 C., while stirring, until the acylation is complete. The productwhich is precipitated in the form of red-violet prisms is filtered offwith suction at 100 C., washed with hot nitrobenzene until the dischargeliquid is clear, then with alcohol and hot water, and dried at 50 C. ina circulating air cabinet.

The other compounds mentioned in Example 1(a-II) are obtained, when the2,5-dichloro-aniline is replaced with equivalent amounts of4-chloro-3-amino-toluene or 2,4,6-trimethyl-aniline, or the1,4-diamino-anthraquinone is replaced with equivalent amounts of5-nitro-1,4- diamino-anthraquinone and the 2,5-dichloro-aniline withequivalent amounts of p-toluidine, 2-chloro-aniline, nbutylamine at 70C. or dodecylamine.

The dyestpffs described in the following Examples are obtained when thecorresponding acid chlorides and amines are used.

The 1,5 dihydroxy 4,8-di-(4-phenylcarbamoyl-benzoylamino)-anthraquinonedescribed in Example 1(a-III) is prepared for example, by introducing 20parts 4,8- diamino-1,S-dihydroxy-anthraquinone at 80 C. with stirringinto a solution of 100 parts terephthalic acid dichloride in 250 partsof aniline-free anhydrous nitrobenzene and 20 parts pyridine, andstirring at 80 to 115 C. until the4,8-diamino-1,S-dihydroxy-anthraquinone is completely acylated. Theprecipitated 1,5-dihydroxy-4,8-di(4-chloroformyl-benzoylamino)-anthraquinone which is present in theform of violet prisms is filtered off with suction, the excess ofterephthalic acid dichloride is washed out with anhydrous nitrobenzene,and the nitrobenzene-moist filter cake is reacted, after dilution with400 parts of anhydrous nitrobenzene, with 60 parts aniline at -160 C,while stirring, until the acylation is complete. The product obtained inthe form of dark-blue prisms is filtered 01f with suction at 100 C.,washed with hot nitrobenzene until the discharge liquid is colourless,then with alcohol and hot water, and dried at 50 C. in a circulating aircabinet.

The other compounds mentioned in Example 1(a-III) are obtained when theaniline is replaced with 26 parts 2-chloro-aniline or 28 partsdodecylamine in the presence of 12 parts N,N-dimethyl-aniline, or whenthe reaction is carried out, instead of with aniline at 140-160 C., with22 parts n-butylamine at 70 to 80 C., or by introducing methylamine at100 C., or when 4,5-diamino-1,8-dihydroxy-anthraquinone is used asstarting material. The other compounds according to the invention areprepared in an analogous way.

EXAMPLE 2 6 parts of finely divided 4-(3-trifluoromethyl benzoylamino) 1(phenylcarbamoyl-benzoylamino)-anthraquinone are rubbed into 100 partsof a nitrocellulose lacquer consisting of 44 parts collodium wool (oflow viscosity, 35%, butanol-moist), 5 parts dibutyl phthalate, 40 partsethyl acetate, 20 parts toluene, 4 parts n-butanol, and 10 parts glycolmonomethyl ether. After spreading and drying, there are obtained bluishred lacquer coats of outstanding fastness to light and overcoating.

The same results are obtained with the use of nitrolacquers containing1015 parts of nitro cellulose, 5-10 l 1 1 parts of plasticiser, and70-85 parts of a solvent mixture, preferably with the use of aliphaticesters such as ethyl acetate or butyl acetate, and of aromatichydrocarbons such as toluene and xylene, and smaller amounts ofaliphatic ethers such as glycol ethers, and of alcohols such as butanol.The plasticisers may comprise, for example, phthalic acid esters such asdioctyl phthalate, dibutyl phthalate; esters of phosphoric acid; castoroil by itself or in combination with oil-modified alkyd resins.

Lacquer coats ofsimilar fastness properties are obtained with the use ofother physically drying spirit, zapon and nitro lacquers, air-dryingoil, synthetic resin and nitro combination lacquers, stoveand air-dryingepoxide resin lacquers, possibly in combination With urea, melamine,alkyd or phenol resins.

Lacquer coats of similar fastness properties and a red shade areobtained with the use of corresponding amounts of finely divided 4- 3-trifiuoromethyl-benzoylamino )-1-[4- (2-chloro-phenylcarbamoyl-benzoylamino] -anthraquinone,

4- (3-trifiuoromethyl-benzoylamino)-1-[4- (4-chloro-phenylcarbamoyl)-benzoylamino] anthraquinone,

4-(3-trifluoromethyl-benzoylamino)-1-[4-(2,5-dich1orophenylcarbamoyl)-benzoy1amino] -anthraquinone,

4-(4-chloro-benzoylamino)-1-(4-dodecylcarbamoyl-benzoylamino)-anthraquinone,

4- (4-nitro-benzoylamino l-(4-phenylcarbamoyl-benzoylamino-anthraquinone,

4-benzoylamino-1-(4-phenylcarbamoyl-benzoylamino anthraquinone,

4-benzoylamino-1-(4-methylcarbamoyl-benzoylamino) anthraquinone,

4-benzoylamino-1- (4-isobutylcarbamoyl-benzoylamino) anthraquinone,

4-benzoylamino-1- [4-(tert.-butyl-carbamoyl)-benzoy1- amino]-anthraquinone,

4-benzoylamino-1- (4-tetradecylcarbamoyl-benzoylamino) -anthraquinone,

4-benzoy1amino-1 [4- 4-chloro-phenylcarbamoyl-benzoylamino1-anthraquinone,

instead of4-(3-trifluoromethyl-benzoylamino)-1-(4-phenylcarbamoyl-benzoylamino-anthraquinone.

Lacquer coats of similar fastness properties and a red shade areobtained with the use of corresponding amounts of finely divided 1,4-di-[4- (butylcarbamoyl -benzoylamino] -anthraquinone,

1,4 di- [4- (isobutylcarbamoyl) -benzoylamino] -anthraquinone,

1,4-di- [4- (tert.-butylcarbamoyl -benzoylamino] -anthraquinone,

1,4-di- [4- (n-dodecylcarbamoyl -benzoylamino] -anthraquinone,

1,4-di- [4- (stearylcarbamoyl -benzoylamino] -anthraquinone,

1 ,4-di- [4- (cyclohexylcarbamoyl) -benzoylamino] -anthraquinone,

1,4-di- [4- (fl-phenyl-ethylcarbamoyl) -benzoylamino] anthraquinone,

1,4-di- [4- (4-dodecyl-phenylcarbamoyl -benzoylamino] anthraquinone,

1,4-di- [4- 4-trifiuoromethyl-phenylcarbamoyl) -benzoylamino]-anthraquinone,

1,4-di- [4- (4-chloro-2-trifluoromethyl-phenylcarbamoyl benzoylamino]-anthraquinone,

1,4-di- [4- 3sulphamoyl-phenylcarbamoyl benzoylaminobanthraquinonc, or

1,4-di-{4- 3- (N-phenylsulphamoyl) -phenylcarbamoyl]benzoylamino}-anthraquinone.

Lacquer coats of similar fastness properties and a yellow shade areobtained with the use of corresponding amounts of finely divided1,5-di-[4-(n-butylcarbamoyl)-benzoylamino]-anthraquinone,

1,5 -di- [4- (isobutylcarbamoyl) -benzoylarnino] -anthraquinone,

1,5-di- [4- tert.-butylcarbamoyl -benzoylamino] -anthraquinone,

1,5-di-[4-(n-dodecylcarbamoyl)-benzoylamino]-anthraquinone,

1,5-di- [4- stearylcarbamoyl -benzoylamino] -anthraquinone,

1,5 -di- [4- (cyclohcxylcarbamoyl -benzoylamino] -anthraquinone,

1,5 -di- [4- p-phenyl-ethylcarbamoyl -benzoylamino] anthraquinone,

1,5-di-[4-(4-dodecyl-phenylcarbamoyl)-benzoylamino]- anthraquinone,

1,5 -di- [4- 4-trifluoromethyl-phenylcarbamoyl) -benzoylamino]-anthraquinone,

1,5-di- [4- (4-chloro-Z-trifiuoromethyl-phenylcarbamoyl)benzoylamino]-anthraquinone,

1,5 -di- [4- (4-sulphamoyl-phenylcarbamoyl)-benzoylamino]-anthraquinone, or

1,5-di-{4- 3- (N-phenylsulphamoyl -phenylcarbamoyl]'benzoylamino}-anthraquinone.

' EXAMPLE 3 5 parts of finely divided4-benzoylamino-1-[4-(n-butylcarbamoyl)-benzoylamino]-anthraquinone areground in parts of a paraffin-free drying, unsaturated polyester resinin a porcelain ball mill. 10 parts monostyrene, 5 parts of amelamine/formaldehyde resin and 1 part of a paste of 40 partscyclohexanone peroxide and 60 parts dibutyl phthalate are well stirredwith this material and, finally, 4 parts of a drier solution (10% cobaltnaphthenate in test benzine) and 1 part of a silicone oil solution (1%in xylene) are added. The mixture is applied to primed wood, and thereis obtained a high-gloss Bordeaux lacquer coat which is fast to waterand weather and eminently fast to light.

If the reaction lacquer derived from unsaturated polyester resin isreplaced with amine-curing epoxide resin lacquers, using dipropylenediamine as amine component, then Bordeaux-coloured lacquer-coats ofoutstanding fastness to weather and blooming are obtained. Similarresults are obtained by use of1,4-di-[4-(4-methyl-phenylcarbamoyD-benzoylamino]-anthraquinone and1,8-di-[4- (methyl phenylcarbamoyl) benzoylamino] anthraquinone.

EXAMPLE 4 (a) 100 parts of a 65% solution of an aliphatic polyester withabout 8% free hydroxyl groups in glycol monomethyl ether acetate areground with 5 parts of finely divided4-(4-chlorobenzoylamino)-1-(4-methylcarbamoyl)-benzoylamino]-anthraquinone and then thoroughly mixed with 44 parts of67% solution of the reaction product of 1 mol trimethylol-propane with 3mol toluylene diisocyanate. Without adverse eifect on the pot time,application of the mixture and reaction of the components leads tohigh-gloss red-violet polyurethane lacquer coats of outstanding fastnessto blooming, light and weather.

Pigmentations of similar fastness are obtained with the use of othertwo-component lacquers derived from aromatic or aliphatic isocyanatesand hydroxyl group-containing polyethers or polyesters, as well as withmoisturedrying polyisocyanate lacquers giving polyurea coats.

(b) Pigmentations of similar fastness properties and a similar shade areobtained when corresponding amounts of 4-(4-methoxy-benzoylamino) -1-[4- (n-butyl-carbamoyl) benzoylamino] -anthraquinone,4-(4-chloro-benzoylarnino -1- [4- (2,4-dichloro-phenylcarbamoyl-benzoylamino] -anthraquinone,

4- (4-chloro-benzoy1amino 1- [4-(2-chloro-5-trifluoromethyl-phenylcarbamoyl)-benzoylamino]-anthraquinone,

1 3 4- (4-chloro-benzoylamino) 1- [4-(4-dodecylphenylearbamoyl)-benzoylamino]-anthraquinone,4(3-chloro-benzoylamino)-anthraquinone)-1-(4-methylcarbamoyl-benzoylamino-anthraquinone, or 4-(2-ch1orobenzoylamino)-1-(4-hexadecylcarbamoylbenzoylamino)-anthraquinone are used, instead ofthe dyestufi mentioned above in Example 4(a).

(c) Pigmentations of similar fastness properties and a similar shade areobtained when corresponding amounts of 1,4-di- [4-(2,3-dichloro-phenylcarbamoyl) -benzoylaminoanthraquinone,1,4-di-[4-(methylcarbamoyl)-benzoylamino]-ant.hra-

quinone,

1,4-di-(4-phenylcarbamoyl-benzoylamino)-ant.hra-

quinone,

1,4-di- [4- (4-chloro-phenylcarbamoyl) -benzoylarnino] anthraquinone,

1,4-di- [4- 2-chlorophenylc arb amoyl) -benzoylamino] anthraquinone,

1,4-di- [4- S-nitro-Z-methyl-phenylcarbamoyl)-benzoylamino]-anthraquinone,

1 ,4-di- [4-(4-anilino-phenylcarbamoyl) -benzoy1amino] anthraquinone,

1,4-di- [4- 4carbamoyl-phenylcarbamoyl) -b enzoylamino]-anthraquinone,or

1,4-di- [4- (pyrenyl-( 1)-carbamoyl)-benzoylaminoanthraquinone are used,instead of the dystutf mentioned above in Example 4(a).

(d) Pigmentations of similar fastness properties and a blue shade areobtained when corresponding amounts of 4-hydroxy-1,4- [4-(2,3-dichloro-pheny1carbamoyl)- benzoylamino] -anthraquinone,

1,5-dihydroxy-4, 8-di- (4-methylcarbamoyl-benzoylamino anthraquinone,

1,5 -dihydroxy-4,8-di(4-phenylcarbamoyl-benzoylamino) anthraquinone,

1 ,5 -dihydroxy-4,8-di- [4- 4chloro -phenylcarbamoyl) benzoylamino]-anthraquinone,

1, 5-dihydroxy-4,8-di- [4-(S-nitro-2-methyl-phenylcarbamoylbenzoylamino] -anthraquinone,

1,5 -dihydroxy-4, 8-di- [4- (4-anilino-phenylc arbamoyl) benzoylamino]-anthraquinone,

1 ,5 -dihydroxy-4,8-di- [4- (4-carbamoyl-phenylcarbamoylbenzoylamino]-anthraquinone, or

1,5-dihydroxy-4,3-di- [4- (pyrenyl- 1 )-carbamoyl) -benzoylamino-anthraquinone are used, intsead of the dyestuff mentioned above inExample 4(a).

EXAMPLE 5 5 parts of a fine paste obtained by kneading 50 parts4-(4-chloro-benzoylamino)-1-[4(4-sulphamoyl-phenylcarbamoyl)-benzoylamino]-anthraquinone with 15 partsof an aryl polyglycol ether emulsifier and 35 parts of water are mixedwith 10 parts of barite as filler, 10 parts of titanium dioxide (rutiletype) as white pigment, and 40 parts of an aqueous disperse dyecontaining about 50% polyvinyl acetate. The paint is spread and, afterdrying, there are obtained red coats of very good fastness to lime andcement and outstanding fastness to weather and light.

The fine paste obtained by kneading is equally suitable for thepigmentation of clear polyvinyl acetate disperse dyes, for disperse dyescontaining copolymers of styrene and maleic acids as binding agents, aswell as for disperse dyes based on polyvinyl propionate,polymethacrylate or butadiene-styrene.

Coats of similar shade and similar fastness properties are obtained whenthe above 4-(4-chloro-benzoylamino)- 1-[4 (4sulphamoyl-phenylcarbamoyl)-benzoylamino]- anthraquinone is replacedwith corresponding amounts of 4-(4-chloro-benzoylamino l-(4-phenylcarbamoyl-benzoylamino -anthraquinone,

4- (4-chloro-benzoylamino -1- [4- 2-chloro-phenylcarbamoyl-benzoylamino] -anthraquinone,

4- (4-chloro-benzoylamino -1- [4- (4-chlorophenylcarbamoyl)-benzoylamino -anthraquinone,

4-(4-chlorobenzoylamino)-1-[4-n-butylcarbamoyl)- b enzoylamino]-anthraquinone,

4-( 2-nitro-benzoylamino) 1- [4- (n-butylcarbamoyl benzoylamino-anthraquinone,

4- 3-nitro-benzoylamino -1- (4-phenylcarbamoylbenzoylamino-anthraquinone,

4- (4-chloro-3-nitro-benzoylamino -1- [4- (heptadecyl- (9 )-carbamoyl-benzoylamino]-anthraquinone,

4- 3 ,5 -dinitro-benzoylamino 1- (4-stearylcarbamoylbenzoylamino-anthraquinone, or

4-(4-ch1orobenzoylamino)-1-(4-cyclohexylcarbamoylbenzoylamino-anthraquinone.

Coats of similar shade and similar fastness properties are obtained whenthe above dyestuff is replaced with corresponding amounts of Blue coatsof similar fastness properties are obtained when the above dyestuff isreplaced with corresponding amounts of 1,5-dihydroxy4,8-di- [4-(4-sulphamoyl-phenylcarbamoyl benzoylamino] -anthraquinone,

1,5 -dihydroxy-4,8-di- (4-phenylcarbamoyl-benzoylamino anthraquinone,

1,5-dihydroxy-4,8-di- [4- (2-chlorophenylcarbamoyl benzoylamino-anthraquinone,

1,5 -dihydroxy-4,8-di- [4- 4-chloro-phenylcarbamoyl benzoylamino]-anthraquinone,

1,5 -dihydroxy-4,8-di- [4- n-butylcarbamoyl -benzoylamino]-anthraquinone,

1,5-dihydroxy-4,8-di [5- (n-butylcarbamoyl -valerylamino]-anthraquinone,

1,5-dihydroxy-4,8-di- [4- 2-nitro-phenylcarbamoyl benzoylamino]-anthraquinone,

1,5 -dihydroxy-4,8-di- [4- 3-nitro-phenylcarbamoyl) benzoylamino]-anthraquinone,

l,5-dihydroxy-4,8-di- [4- (4-nitro-phenylcarbamoyl)benzoylamino]-anthraquinone, or

1,5 -dihydroxy-4,8-di- [4- 3,4-dichloro-phenylcarbamoyl) benzoylamino]-anthraquinone.

EXAMPLE 6 10 parts of a pigment paste mentioned in Example 5 are mixedwith a mixture of 5 parts of chalk and 5 parts of 20% size solution. Ared wall paper coating colour is obtained yielding coats of outstandingfastness to light. For the preparation of the pigment paste there mayalso be used other non-ionic emulsifiers, such as the reaction productsof nonylphenol with ethylene oxide, or ionic wetting agents, such as thesodium salts of alkylaryl-sulphonic acids, for example ofdinaphthyl-methane-disulphonic acid, sodium salts of substitutedsulphofatty acid esters, and sodium salts of paraflin-sulphonic acids incombination with alkyl polyglycol ethers.

EXAMPLE 7 A mixture of 65 parts polyvinyl chloride, 35 parts diisooctylphthalate, 2 parts dibutyl tin mercaptide, 0.5 parts titanium dioxide,and 0.5 parts 4-(4-chloro-benzoylamino l- [4- (l-chloro-phenylcarbamoyl-benzoylamino] 15 anthraquinone, which has been finely divided bygrinding with sodium chloride in the presence of test benzine, iscoloured on mixing rolls at 165 C. An intensely Bordeaux-coloured massis obtained, which can serve for the production of foils or mouldings.The colouration is characterised by excellent fastness to light and verygood fastness to plasticisers.

Colourations of a red shade and similar fastness properties are obtainedwhen the above 4-(4-chloro-benzoylamino) -l-[4-(2-chloro-phenylcarbamoyl)-benzoylamino] anthraquinone is replacedwith corresponding amounts of 4- (4-chlorobenzoylamino 1- [4- (2,5-dichloro-phenylcarbamoyl)-benzoylamino]-anthraquinone,4-(4-chloro-benzoylamino) -1- [4-(4-trifiuoromethylphenylcarbamoyl)-benzoylamino] -anthraquinone, 4- (4-chloro-benzoylamino l- [4-(4-methoxy-phenylcarb amoyl -benzoylamino -anthraquinone,

4- (4-chloro-benzoylamino)-1- [4-(3-sulphacyclopentyl-S,S-dioxide-carbamoyl) -benzoylamino] -anthraquinone, 4-( 3-trifiuoromethyl-benzylamino 1- 4-butylcarbamoy1-benzoylamino)-anhtraquinone, or 4-(4-nitro-benzoylamino )-1-(4-phenylcarbamoylbenzoylamino )-anthraquinone.

Colourations of a similar shade and similar fastness properties areobtained when the above dyestufi' is replaced with corresponding amountsof 1,4-di-[4-(n-butyl-carbamoyl)-benzoylamino]-anthraquinone,

1,4-di- [4- (isobutylcarbamoyl) -benzoylamino] -anthraquinone,

1,4-di-[4-(n-dodecylcarbamoyl)-benzoylamino]-anthraquinone,

1,4-di- [4- (4-chloro-phenylcarbamoyl -benzoylamino] anthraquinone,

1,4-di- [4- (4-carbamoylphenylcarbamoyl) -benzoylamino] -anthraquinone,

1,4-di- [4-( 4-sulphamoyl-phenylcarbamoyl -benzoylamino]-anthraquinone,

1,4-di- [4- 3-hydroxy-propyl-carbamoyl -benzoylamino] anthraquinone,

1,4-di- [4- (4-acetyl-phenylcarbamoyl -benzoylamino] anthraquinone.Colourations of a yellow shade and similar fastness properties areobtained when the above dyestuff is replaced with 4-hydroxy-1, 5-di- [4-(butylcarbamoyl -benzoylamino] anthraquinone,1,5-di-(4-phenylcarbamoyl-benzyolamino)-anthraquinone,

1,5 -di- ['4- methylcarbamoyl benzoylamino] -anthraquinone,

1,5-di-(S-phenylcarbamoyl)-benzoylamino-anthraquinone,

1,5-di-[3-(4-chloro-phenylcarbamoyl)-benzoy1amino]- anthraquinone,

1,8-di- [4- (methylcarbamoyl -benzoylamino] -anthraquinone,

1,8-di-(4-phenylcarbamoyl-benzdylamino)-anthraquinone,

EXAMPLE 8 0.2 parts of finely divided 4-(4-chloro-benzoylamino)-1-(4-phenylcarbamoyl-benzoylamino)-anthraquinone are mixed with parts ofa polyethylene, polypropylene or polystyrene granulate. The mixture caneither be immediately injection-mpulded at 220 to 280 C. in an injectionmoulding machine, or it can be worked up in an extruder to producecoloured rods, or on mixing rolls to produce coloured rough sheets. Ifdesired, the rods or rough sheets are granulated and injection-mouldedin an injection-moulding machine.

The red mouldings are very fast to light and migration. In a similarmanner, synthetic polyamlides of caprolactam or adipic acid andhexamethylene diamine or condensation products of terephthalic acid andethylene glycol can be coloured at 280-300 C., possibly under a nitrogenatmosphere. Similar red moldings are obtained by use of1,4-di-[4-(n-butylcarbamoyl)-benzoylamino]-anthraquinone, and similarlyblue moldings are obtained by use of1,5-dihydroxy-4,8-di-(methylcarbamoyl-benzoylanrino -anthraquinone.

EXAMPLE 9 1 part of finely divided4benzoylamino-1-(4-phenylcarbamoyl)-benzoylamino]-anthraquinone, 10parts titanium dioxide (rutile type) and 100 parts of a copolymerderived from acylonitrile-butadiene-styrene and present in powdered formare mixed and coloured on mixing rolls at -180 C. A wine-red rough sheetis obtained, which is granulated and injection moulded at ZOO-250 C. inan injection-moulding machine. There are obtained wine-red mouldings ofvery good fastness to light and migration and excellent thermalstability.

In a similar manner, but at temperatures of 180-220 C. and without theaddition of titanium dioxide, synthetic materials based on celluloseacetate, cellulose butyrate and mixtures thereof are coloured withsimilar fastness properties. Similar wine-red moldings are obtained byuse of 1,4di[4-(4-methyl-phenyl-carbamoyl)-benzoylamino]-anthraquinoneand similar orange-colored moldings are obtained by use of1,5-di-[4-(4-methyl-phenylcarb amoyl-benzoylamino] -anthraquinone.

EXAMPLE 10 0.2 parts 4-benzoylamino 1[4-(3,4-dichloro-phenylcarbamoyD-benzoylamino] -anthraquinone in finelydivided form are mixed with 100 parts of a synthetic material based onpolycarbonate in an extruder or a kneading worm at 250280 C. and workedup into a granulate. A violet transparent granulate of outstandingfastness to light and thermal stability is obtained. Similar violettransparent granulates are obtained with 5,8- dihydroxy 1,4 di-(4-phenyl-carbamoyl-benzoylamino)- anthraquinone and blue transparentgranulates are obtained with 1,5-dihydroxy-4g8-di-(4-phenyl-carbamoyl)-benzoylaminoanthraquinone.

EXAMPL'E ll'l 90 parts of a slightly branched polypropylene glycol witha molecular weight of 2500 and a hydroxyl number of 56, 0125 partsendoethylene-piperazine, 0.3 parts tin (II) octoate, 1.0 part of apolyether siloxane, 3.5 parts of water, 12.0 parts of a dispersion of 10parts of finely divided4-benzoylamino-1-('4-methylcarbamoyl)-benzoylaminoJ-anthraquinone in 50parts of the stated polypropylene glycol are well mixed with one anotherand subsequently intimately mixed with 45 parts toluylene diiso- 17cyanate (80% 2,'4- and 2,6-isomer), and poured into a mould. The mixturebecomes turbid and formation of foam takes place. After 70 seconds, anintensely wine-red soft polyurethane foam has formed the pigmentation ofwhich has outstanding fastness to light.

Reddish blue polyurethane soft foams of a similar lightfast pigmentationare obtained when the 4-benzoylaminol (4methylcarbamoyl-benzoylamino)-anthraquinone is replaced withcorresponding amounts of 2-bromo-4- (4-methyl-anilino -1- (4-phenylcarbamoylbenzoylamino) -anthraquinone,

2-bromo-4-(4-methy1-2,G-diethyl-anilino -1-(4-phenylcarbamoyl-benzoylamino anthraquinone,

4-aniline-1- [4- (4-methyl-cyclohexylcarbamoyl) -benzoylamino]-anthraquinone,

4-anilino-1-[4-(hexahydrobenzylcarbamoyl)-benzoylamino] -anthraquinone,

4-anilino-*1- [4- 2-hydroxy-ethylcarbamoyl -benzoylamino]-anthraquinone,

4-anilino 1- [4--( 3-hydroxy-propylcarbamoyl) -benzoylamino]-anthraquinone, or

4-anilino-l- [4- 3-chloro-phenylc arbamoyl) -benzoylamino]-an'thraquinone.

'Reddish blue polyurethane soft foams of a similar light-fastpigmentation are obtained when the above dyestulf is replaced withcorresponding amounts of 1,5-di- [4- (4-methoxy-phenylcarbamoyl)-benzoylamino] anthraquinone,

1,5 -dihydroxy-4,8-di- ['4-(methyl-carbamoyl -'benzoylamino]-anthraquinone,

'1,5-dihydroxy-4, 8-di- [4- n-butylcarbamoyl) -benzoylamino] -anthraquinone,

1,5 -dihydroxy-4,8-di- [4-n-dodecylcarbamoyl-benzoylamino1-anthraquinone,

1,5 -dihydroxy-4,8-di- [4- (4-chloro-phenylcarbamoyl) benzoylamino]-anthraquinone,

1,5-dihydroxy-4,8- [4 (4-carbamoyl-phenylcarbamoyl)benzoylamino]-ar1thraquinone,

1,5 -dihydroxy-4,8-di[4-(4-sulphamoyl-phenylcarbamoyl)-benzoylamino]-anthraquinone, or

1,8-dihydroxy-4,5-[4-(4-sulphamoyl)-phenylcarbamoyl)-benzoylamino]-anthraquinone.

Reddish blue polyurethane soft foams of a similar light-fastpigmentation are obtained when the above dyestuff is replaced withcorresponding amounts of 1,4-di- [4- 4-methoxy-phenylc arb amoyl)-benzoylamin] anthraquinone,

1,4-di-{4- [-2- (2-hydroxy-ethyl-amino -ethylca1-bamoyl] benzoylamino}-an'thraquinone,

1,4-di- 9-methylcarbamoyl-octadecanoylamino) -anthraquinone,

1,4-di- 3 (-4-su1phamoyl-phenylcarbamoyl -2-hydroxypropionylamino]-anthraquinone,

1,4-di- [3 3-carbamoyl-phenylcarbamoyl) -2-acety1aminopropionylamino]-anthraquinone,

1,4-di- 2,5-dimethoxy-4-phenyl-carbamoyl-benzoyl) amino) -anthraquinone,

1,4-di 4-chloro-3 -methylcarb amoyl-benzoylamino anthraquinone,

1,4- di- (2,5 -difluoro-4-butylcarbamoyl-b enzoylamino) anthraquinone,or

1,4-di- [2,3,5,6-tetrachloro-4- (4-methyl-phenylcarbamoyl)-benzoylamino] -anthraquinone.

EXAMPLE 12 90 parts of a slightly branched polyester of adipic acid,diethylene glycol and trimethylol-propane with a molecular weight of2000 and a hydroxyl number of 60 are mixed with the followingcomponents: 1.2 parts dimethyl-benzylamine, '25 parts sodium castor oilsulphate, 2.0 parts of an ethoxylated benzylated hydroxydiphenyl, 1.75parts of water, '12 parts of a paste prepared by grinding 10 parts offinely divided 4-(4-chloro-benzoylamino)-l- [4 (4carbamoyl-phenylcarbamoyl)-benzoylamino]- anthraquinone in 50 parts ofthe polyester mentioned above. After mixing, 40 parts toluylenediisocyanate (65% 2,4- and 35% 2,6isomer) are added with stirring andthe mixture is poured into a mould and foamed. After 60 second-s, ared-violet soft polyurethane foam has formed the colouraton of which ischaracterized by very good fastness to light. Green-blue colourations ofsimilar fastness to light are obtained by using corresponding amounts of4-anilin0-1- [4- (2,3 -dichlorophenylcarb amoyl -benzoylamino]-anthraquinone,

4-anilino-l- [4-( 2,S-dichloro-phenylcarbamoyl) -benzoy1- amino]-anthraquinone,

4-anilinol- [4 (4-carb amoyl-phenylcarb amoyl) -b enzoylamino]-anthraquinone,

4- 4-methoxy-anilino l [4 (n-b utylcarbamoyl -benzoy1- amino]-anthraquinone, or

4- (4-methylanilino) -'l- [4- (n-butylcarbamoyl) -benzoylamino]-anthraquinone,

instead of the aforesaid 4-'(4-chloro-benzoylamino) 1- [4 (4carbamoyl-phenylcarbamoyl) benzoylamino]- anthraquinone.

Red colourations of similar fastness to light are obtained when the4-(4-chloro-benzoylamino)-1-[4-(4-carbamoyl)-phenyl-carbamoyl)-benzoylamino]anthraquinone is replaced with corresponding amounts of4-chloroacetylamino-1- (4-b enzylcarb amoyl-b enzoylamino-anthraquinone,

4-valerylaminol- [4- (2-phenyl-ethylcarbamoyl)-benzoylamino1-anthraquinone,

4-ste aroylaminol- [4- (4-carbethoxyphenylcarbamoyl benzoylamino]-anthraquinone,

4-( 3-sulphamoyl-b enzoylamino l- (4-phenylcarbamoylbenzoylamino-anthraquinone, or

2-methyl-4- (4-chlorobenzoylamino l- (4-phenylcarbamoyl-benzoylamino)-anthraquinone.

Green-blue colourations of similar fastness to light are obtained byusing corresponding amounts of 1,4-di- [4-phenylcarbamoyl-phenylazoxyl)-benzoylamino] -anthraquinone,

1,4-di- [4- (4-butylcarb amoyl-phenyl-hydrazino) benzoylamino]-anthraquinone,

1,4,-di (4-methyl-carbamoyl-benzyl) -benzoylamino] anthraquinone,

1,4-di- [4- (4-benzoy1-phenylcarbamoyl) -benzoylamino] anthraquinone,

1,4-di- 5- (4-methoxy-phenylcarb amoyl) -furanoyl- 2) amino]-anthraquinone,

1,4-di- [5- (2-nitro-4-carbamoyl-phenylcarbamoyl)-thiophenyl- (2 -amino]-anthraquinone,

1,4-di-{4- [4- 4'-methylcarbamoyl-biphenyl- (4) -azo) phenyl]-benzoylamino}anthraquinone,

1,4-di- [2-methoxy-4-phenylsulphonyl-phenylcarbamoyl benzoylamino]-anthraquinone,

1,4-di- [2,4-dicarbamoyl-phenylcarbamoyl) benzoylamino] -anthraquinone,

1,4-di- [4-( 6-carbarnoyl-naphthyl- (2) -carbamoyl)-benzoylamino1-anthraquinone,

1 ,4-di-{4- [2-chloro-5- (2-hydroxyethyl-sulphamoyl) phenylcarb amoyl]benzoylamino}-anthraquinone,

1,4-di- [4- (Z-carbamoyl-5-sulphamoyl-phenylcarbamoyl) benzoylamino-anthraquinone,

1,4-di-{4- [4- 4-carbamoyl-phenylazo) -phenylcarbamoyl]-benzoylamino}-anthraquinone, and

1,4-di- (2,3 ,5 ,6-tetrafluoro-4-phenylcarbamoyl-benzoylamino)-anthraquinone gives red-violet colouration.

Green-blue colourations of similar fastness to light are obtained byusing corresponding amounts of 3-chloro-1,5-di- (4-methyl-anilino)-4,8-di- [4- (2,3-dichloro-phenylcarb amoyl) -benzoylamino]-anthraquinone,

S-amino-1-hydroxy-4,8-di- [4- 2, 5-di-chloro-phenylcarbamoyl) -b enzoylamino] -anthraquinone,

2,6-dibrom-4,8-dihydroxy-1,5-di- [4- (4-carbamoylphenylcarbamoyl) -benzoylamino] -anthraquinone,

4, S-diamino- 1,5 -di- [4- (n-butylcarbamoyl) -benzoylamino]-anthraquinone, and

l-b enzoylamino-4,5-di- [4- (4-carbamoyl-phenylcarbamoyl) -benzoylamino] -anthra quinone gives red-violet colouration.

Green-blue colourations of similar fastness to light are obtained whenthe above dyestuif is replaced with cone sponding amounts of one of thedyestulfs which are obtained 'by proceeding according to Example 1(c),but using, instead of 20 parts 1,4-diamino-anthraquinone, 29 parts ofone of the two dyestuffs obtained when 1,5-dihydroxy-4,8-diaminoor1,8-dihydroxy-4,S-diamino-anthraquinone is brominated in sulphuric acidin such a manner that the reaction product contains approximately onebromine atom per mol of 1,5-dihydroxy-4,8-diaminoor1,8-dihydroxy-4,S-diamino-anthraquinone.

EXAMPLE 13 A printing ink prepared by grinding 35 parts of finelydivided 4 benzoylamino 1-(4-phenylcarbamoyl-benzoylamino)-anthraquinoneand 65 parts linseed oil and adding 1 part of a desiccator(Co-naphthenate, 50% in test benzine) yields red offset prints of highbrilliancy and strength of colour and very good fastness to light andlacquering. The use of this printing ink in book printing, heliographicprinting, lithographic printing or steel engraving printing leads to redprints of similar fastness properties. If the pigment is used forcolouring pastes for sheet metal printing, or low viscosity pastes forheliogravure and printing inks, red prints of similar fastnessproperties are obtained.

If the 4-benzoylamino 1-(4-phenyl carbamoyl-benzoylamino)-anthraquinoneis replaced with corresponding amounts of 4- 3-chloro -benzoylamino) 1(2,5 -dichloro-4-phenylcarbamoyl-benzoylamino -anthraquinone,

4-benzoylamino-1- (4-hydroxy-3-phenylcarbamoyl-benzoylamino)-anthraquinone,

4- 4-chloro-b enzoylamino) 1- 6-phenylcarbamoylnaphthoyl- (2) -amino-anthraquinone,

4- (4 chloro-b enzoylamino l- [4- (4-phenylcarb amoylphenyl) -benzoylamino] -anthraquinone,

4-benzoylamino-1- [4- (4-phenylcarbamoyl-phenoxy benzoylamino]-anthraquinone,

4-benzoylamino-1- [4- (Z-phenylcarbamoyl-b enzoyl) benzoylamino]-anthraquinone,

4-benzoylamino- 1- [4- (4-phenylcarbamoyl-phenylsulphonyl) -benzoylamino] -anthraquinone,

4- (4-nitro-benzoylamino)-1- (-phenylcarbamoyl-valerylamino)-anthraquinone,

then prints of a similar shade and similar brilliancy and fa-stness areobtained.

If the above pigment is replaced with corresponding amounts of 1,4-di-[4- n-do decylcarbamoyl) -benzoylamino] -anthraquinone,

Z-phenoxy- 1,4-di- [4- (4-trifluoromethyl-phenylcarbamoyl)-benzoylamino] -anthraquinone,

1,4-di- [5- n-butylcarbamoyl) -valerylamino] -anthraquinone,

1,4-di- [4- (n-butylcarb amoyl -benzoylamino] anthraquinone,

1,4-di- [2,5-dichloro-4-(n-dodecylcarbamoyl) -benzoylamino]-anthraquinone,

, 1,4-di- [4-hydroxy-3-(n-dodecylcarbamoyl)-benzoylaminoJ-anthraquinone,

1 ,4-di- [6- n-dodecylcarb amoyl) -naphthoyl- (2) -amino]-anthraquinone,

1,4-di- [4- [4- ndodecyl-carbamoyl) -phenyl] -b enzoylamino]-anthraquinone,

1,4-di- [4- [4- (n-dodecylcarbamoyl) -phenoxy] -benzoylamino]-anthraquinone,

1,4-di- [4- [2- (n-dodecylcarb amoyl) -benzoyl] -benzoy1- amino]-anthraquinone or 1,4-di- [4- [4- (n-dodecylcarb amoyl)-phenylsulphonyl] benzoylamino] -anthraquinone,

then prints of a similar shade and similar brilliancy and fastness areobtained.

If the above pigment is replaced with corresponding amounts of 1,5-dihydroxy-4,8-di- 4-phenylcarbamoyl-benzoylamino) -anthraquinone,

1,5 -dihydroxy-4,8-di- (4-methylcarb amoyl-benzoylamino -anthraquinone,

1, 5-dihydroxy-4, 8-di- [4- (n-butylcarb amoyl-benzoylamino]-anthraquinone,

1,5 -dihydroxy-4,8-di- 5 (n-butylcarbamoyl) -valerylamino]-anthraquinone,

1,5-dihydroxy-4,8-di- [2,5-dichloro-4- (n-dodecylcarbamoyl) -benzoylamino] -anthraquinone,

1, 5-dihydroxy-4, 8-di- (4-hydroxy-3 -phenylcarbamoyl benzoylamino)-anthraquinone,

1,5 -dihydroxy-4, 8-di- 6-phenylcarbamoyl-naphthoyl- (2 amino)-anthraquinone,

1,5 -dihydroxy-4, 8-di- [4- 4-phenylcarbamoyl-phenyl) benzoylamino]-anthraquinone,

1,5 -dihydroxy-4,8-di- [4- 4-phenylcarb amoyl-phenoxy) benzoylamino]-anthraquinone,

1,5 -dihydroxy-4, 8-di- [4- (Z-phenylcarbamoyl-b enzoyl) benzoylamino]-anthraquinone, or

1,5-dihydroxy-4, 8-di- [4- 4-phenylcarbamoyl-phenylsulphonyl)-benzoylamino] -anthraquinone,

then prints of a blue shade and similar fastness are obtained.

EXAMPLE 14 A printing paste is prepared from 10 parts of a pigment finepaste described in Example 5, parts of 3% tragacanth, 100 parts of a 50%egg albumin solution and 25 parts of a non-ionic wetting agent. A fabricof textile fibres is printed, steamed at 100 C., and a red or blue printis obtained, which is characterised by excellent fastness properties,especially fastness to light. Instead of tragacanth and egg albumin,other binding agents suitable for fixation on the fibre, for example,those derived from synthetic resin, British gum or cellulose glycollate,can be used in the printing mixture.

EXAMPLE 15 A mixture of 100 parts of light crepe, 2.6 parts sulphur, 1part stearic acid, 1 part mercapto-benzothiazole, 0.2 partshexamethylene-tetramine, 5 parts zinc oxide, 60 parts chalk and 2 partstitanium dioxide (anatase type) is coloured on mixing rolls at 50 C.with 2 parts 4-benzoylamino 1 [4 (n.- butylcarbamoyl)-benzoylamino]-anthraquinone and then vulcanized at C. for 12 minutes. A wine-redvulcanization product of very good fastness to light is obtained.

A wine-red product is obtained also by use of 1,4-di-[4 (3,5 dichlorophenyl carbamoyl) benzoylamino]- anthraquinone and a yellow product isobtained with 1,8- di- [4 (3,5 dichlorophenyl carbamoyl)-benzoylamino]-anthraquinone.

EXAMPLE 16 100 parts of a 20% aqueous paste of4-(3-trifluoromethyl-benzoylamino) 1 [4-(4-nitrophenylcarbamoyl)-benzoylamino]-anthraquinone, prepared, for example, by dissolving thedyestufi in 96% sulphuric acid, pouring the solution on to ice,filtering and washing with water until neural, are admixed in a stirrerwith 22,500 parts of an aqueous, approximately 9% viscose solution. Thecolored mass is stirred for 15 minutes, subsequently de-aerated andsubjected to a spinning and desulphurizing process.

Orange-red filaments or foils of very good fastness to light areobtained. Also similar shades are obtained by use of 1,4 di[4-(2-methyl-benzothiazolyl-(6)-carbamoyl)-benzoylamino]-anthraquinone.Yellow filaments or foils of good fastness to light are obtained with1,5-di- [4 (4 sulfamoyl-phenyl-carbamoyl)-benzoylamino]- anthraquinone.

Filaments or foils with a wine-red pigmentation of similar fastness areobtained when a 20% solution of acetyl cellulose in acetone, or a 15-25%solution of polyacrylonitrile in dimethyl formamide, which has beencolored with finely divided 4- (4-chloro-b enzoylamino l-[4-chlorophenylcarbamoyl] -benzoylamino] -anthraquinone,

1,4-di- [4- 4-sulfamoyl-phenyl-carbamoyl) benzoylamino]-anthraquinone,or

4-hydroxy-1,5-di [4-(4sulfamoyl-phenyl-carbamoyl)-benzoylamino]-anthraquinone,

is subjected to a dry spinning process.

EXAMPLE 17 10,000 parts of paper pulp containing 4 parts cellulose per100 parts are treated in a hollander for about 2 hours. During thistime, there are added at intervals of 15 minutes 4 parts of rosin size,then 30 parts of an approximately 15% pigment dispersion obtained bygrinding 4.8 parts4-(3-trifluoromethyl-benzoylamino)-l-[4(4-chlorophenylcarbamoyl)-benzoylamino]-anthraquinonewith 4.8 parts dinaphthyl-methane-disulphonic acid and 22 parts of waterin a ball mill, and then parts aluminum sulphate. After finishing in apaper machine, a bluish red paper of outstanding fastness to light isobtained. Similar results are obtained with1,4-di-[4-(n-butyl-carbamoyl)-benzoy1- amino]anthraquinone and1,5-dihydroxy-4,8-di-(4-methyl-carbarnoyl-benzoylamino) -anthraquinone.

EXAMPLE 18 The blue and red pigmented papers produced according toExample 17 are impregnated with a 55% solution of an urea-formaldehyderesin in n-butanol and stoved at 140 C. A bluish red laminate paper ofvery good fastness to migration and outstanding fastness to light isobtained.

A laminate paper of similar fastness properties is obtained bylaminating a paper which was printed by the heliogravure process with aprinting paste containing the red pigment fine pastes described inExample 5 and watersoluble or hydrolysable binding agents.

EXAMPLES 19-212 Fast pigmented stoving lacquers of the shades stated inthe following Table are obtained according to Example 1(a), but usingcorresponding amounts of the finely divided dyestufi stated in theTable, instead of 4-(4-chloro-benzoylamino) 1[4-(4-chloro-phenylcarbamoyl)- benzoylaminol-anthraquinone:

EXAMPLE-C ontinued Ex. Dyestufi Shade 28-4-(4-chloro-benzoylamino)-l[4(4-trifluoromethyl- Bluishphenylcarbamoyl)benzoylaminoLanthraquinone. red.

29.... 4-(4eh1oro-benzoylamino)-1-[4-(3-sulphan1oylphenyl- Red.

earbamoyl)-benzoylamin01-anthraquinone.

30. 4-(4-chloro -benzoylamino)-l-[4-(3-thia-cyclopenty1- Red.

S,$-d1ox1de-carbamoyl)-beuzoylamin0lanthraqumone.

31- 4-beuzoylamino-1-[+(Z-chlormphenylcarbamoyl)- Yellowishbenzoylamino1-anthraquinoue. red.

32- 4-benzoylamino-1-[4-(3-chloro-phenylcarbamoyl)- Red.

beuzoylamino1-anthraquinone.

33- 4-benzoylamino-1-[4-(2,5-dichloro-phenylcarbamoyl)- Red.

benzoylamino1-anthraquinone.

34- 4-benzoylamino-l-[4-(4-nitro-phenylcarbamoyl) Red.

benzoylamiuo]anthraquinone.

35. 4-(4-methoxy-benzoylamino)-l-[4-(2,5-diehloro- Bluishphenylearbamoyl)benzoylamino1-anthraquinone. red' 36.4-(4methoxy-benzoylamino)-1-[4=-(4nitrophenyl- Violet.

carbamoyl)-benzoylamino]anthraquinone.

37. 4-(S-tnfluoromethyl-benzoylamino)-1-(4-phenyl- Bluishcarbamoyl-benzoylamino)-anthraquinone. red.

38- 4-(3tritluoromethyl-benzoylamino)-1-[4-(4'ch1oro- Do.phenylcarbamoyl)-benzoylamino]-anthraquinone.

39. 4-(4-nitro-benzoylarnino)-1-(4-methylcarbamoyl- Do.

benzoy1amino)-anthraquinone.

40. 4-(4-nitro-beuzoylamino)-1-[4- (n-butylcarbamoyl)- Dbenzoylaminolanthraquinone.

41- 4-(4-nitro-benzoylamino)1-[4-(n-dodecylcarbarnoyb- Do.

benzoylaminol-anthraquinone.

42. 4-(4nltro-benzoylami no) -l-[4-(24:h10rophenylcar- Red.

bamoyl) -benzoylamino1-anthraquinone.

43 4(4nitro-benzoy1amino)-1-[4-(4-chlorophenylcar- Bluishbamoyl)-benzoylamino]-anthraqu1none. ed,

44...- 4-(4-nitro-benzoylamino)-l-[4-(2,5-d1ch1oropheny1car- Do.

bamoyl)-benzoylarnino]anthraquinone.

45-..- 4-(2,4-dichloro-henzoylamino)-l- [4-(5-carboxy- Red.

pentylcarbamoyl)-benzoylaminoe-anthraquinone.

46. 4-(2,4-dichloro-benzoylamlno) -1-{ 4 2-hydroxy- Red.

ethylamino)-ethylcarbamoyll-benzoylamino)- anthraquinone.

47.-... -(2,4-dieliloro-benzoylamino)-l[4-(3-butoxy- Red.

propylcarbamoyl)-benzpylamino]-authraquinone.

4-(2,4-diehloro-benzoylarmno)-1-[4(3,5-dich10r0- Red.

henylcarbamoyl)-benzoylamino1-anthraquinone.

49.... 4- 2,5-diehl0ro-benzoylamino)-l-[4-(2-ethy1mereapto- Red.ethylcarbamoyl)-benzoylaminol anthraquinone.

50. 4-(2,5oichloro-benzoylamino) -1-[4-(benzoylmethyl- Red.

earbamoyl)-benzoylaminolanthraquinone.

51. 4-(2.54lieh1oro-benzoylamino) -l-[4(2,3,5trichloro- Yellowishphenylcarbamoyl)-benzoylamin0]-anthraquinone. red.

52-... 4-(4-methyl-benzoylamino)-1-[4-(5-chloro-2-nitro- Red.

phenylearbamoyl)-benzoylam1no] anthraquinone.

53-.-. 4-(4-methyl-benzoylamlno)1-[4-(2A-d1nitropheny1- Red.

carbamoyl)-benzoylaminol-anthraqulnone.

54..-. 4-(4-methyl-benzoylamlno)-1[4-(6-br0mo-2,4-dinitro- Red.

phenylcarbamoyl)-benzoylamlno]-authraquiuone.

55- 4-(4-methy1-benzoy1amino)-1-[4-metl1y1pheny1ear- Red.

bamoyl)-benzoylamlnol anthraqulnone.

56--.- 4-acetylamino-l-[4 (4-methyl-phenylearbamoyl)- Red.

benzoylaminol-anthraquinone.

57-... fi-nitro--benzoylamlno-l-[4-(4methyl-phenyl- Red,

carbamo l)-benzoylaminol-anthraquinone.

58-.... 2-bromo-1-g1-(4-methyl-phenylcarbamoyl)-benzoyl- Red.arriino]4-(methyl-benzenesulphamldo)-ant;hra-

q none.

59..... 4-(-trifluoromethyl-benzoylamino)-1-[4-(4-methyl- Red.

phenylcarbamoyl)-benzoylamino]anthraquinone.

60.--. 4-beuzoylamino-1-[4-(5-chloro-2-trifluoromethyl- Red.

phenylcarbamoyl)-benzoylamino]-anthraqu1none.

61. 4-benzoylamino-1- +(5-nitro-2-methy1-phenylcar- Red.

bamoyl)-benzoy..amino]-anthraqumone.

62---. benzoylsmino-l- 4-(2-ch1oro-5-methy1-pheny1car- Red.

bamoyl)-benzoy;amino]-anthraquinone.

63-.-- 4-benzoylamino-l-lt(3,5-bis-trlfluoromethylphenyl- Red.

carbamoyl)-benzoylamlng-anthraquinone.

64---- 4-benzoylamino-1-[4-(2,4,6-t methyl-phenylcar- Red.

barnoyl)-benzoylaminol-anthraquinone.

65.... 4(3-ch10ro-benzoylamino)-1-[4-(4-methy1-3,6-dlethyl- Red.

phenylcarbamoyl)benzoylaminol-anthraqulnone.

66-.. 43ch1oro-benzoylamino)-1-[4-(5,6,7,8tetrahydro- Red.naphthyl-(l)-carbamoyl)-benzoylaminol-anthraquiuone.

67---.. 4-(3ch1oro-benzoylamino)-1-[4-(4'cyclohexy1pheny1- Red.

carbamoyl)-benzoylamino]anthraquinone.

68---. 4-(3-chloro-benzylamino)-1-(naphthyl-(1)-carbam- Red.

oyl-benzoylamino)anthraquinone.

69-.-. 4-(4-chloro-benzoylarnino)-1-(4-anthracenyl-(2)-ear- Red.

barnoyl-benzoylamino)-anthraquinone.

70-... 4-(4ch1oro-benzoylamino)-1-(4.pyrenyl-(l)-carbam- Red.

oyl-benzoylamino)-anthra uinone.

71-..- 4-(4-ch10robenzoy1amino)-1-4(4-anilinophenylcar- Red.

bamoyD-benzoylamino]-anthraquinone.

72.... 4-(4-chloro-benzoylamino)-1-[4-(4-phenoxyphenyl- Red.

carbamoyl)-benzoylamino]-anthraquinone.

73...- 4-(4nitrobenzoy1amino-1-{4-[4-(4methylanilino) Red.

phenylcarbamoyl]-benzoylaminol-anthraquinone.

74-.-- 4-(4-nitro-benzoylamino)-1-{4[4-(4-rnethoxyanilino)- Red.

phenylearbamoyll-benzoylamino l-anthraquinone.

75..-. 4-(4 nitro-benzoy1amino)-1-[4-(4-methylsulphonyl- Red.

phenylcarbamoyl)-benzoylamino]-anthraquinone.

76--.- 4-(3-trifiuoromethyl-benzoylamino)1-[4-(2-methoxy- Red.

5-phenylsulphouyl-phenylearbamoyl)-benzoylamino]-anthraquinone.

77--.- 4-(3-t1ifiuoromethyl-benz0ylarnino)-1-[4-( t-benzoyl- Red.

phenylcarbamoyl)-benzoylemino1-anthraquinone.

78- 4-(3-trifiuoromethyl-benzoylamino)-l-[4-(4-acetyl- Red.

phenylearbamoyl)-beuzoylamiuo]-anthraquinone.

then fast laminated papers of the specified shades are obtained.

Ex. Dyestufl Shade 368. 4-(4-chloro-benzoylamino)-1-(4-methy1earbamoyl-Redbensoylamino)-anthraquinne. violet.

369--. 4-(4-ehloro-banzoylaminoH-[4-(4-r1itrophenylear- Red.

bamoyl)-benzoylarnino]-anthraquinune.

370- 4-benz0y1am1n0-1-[4-(n-butyl-carbamoyD-ben- Bordeaux.

zoylamlnol-anthraquinone.

371 4-benzoylamino1-(4-phenylearbamoyl-benzoyl Red.

amin0)-anthraquinone.

372. 4-benzoy1amino-1-[4-(2-ch10ro-pheny1earbam0yl)- Red.

benzoylaminol-anthraquinone.

373--- 4-benzoylamin0-1-I4-(4-nitrohenylcarbamoyD- Red.

benzoylamino]-anthraquinone. l

374-.- 4-(3-trifluoromethyl-benzoylamino)-1-(4-butyl- Red.

carbamoyl-benzoylamino)-anthraquinone.

375--. 4-(4-nitr0-benzoy1am1no)-1-[4-(4-eh1oropheny1car- Red.

bamoyD-benzoylaminol-anthraquinone.

376. 2-bromo-1-[4-(4-chloro-phenylcarbamoyl)-ben- Red.

zoylamino]4-(4-methy1-benzenesulphamido)- anthraquinone.

377- 1,4431-[4-(2,3dichloro-pheny1carbamoyD-ben- Bluishzoylaminol-anthraquinone. red.

378-.. 1,4-di-[4-(2,5-dichloro-phenylcarbamoyl)-ben- 'Violet.

zoylaminol-anthraquinone.

379. 1,4-d1-[4-(2-ch1oro-5-trlfluoromethyl-phenylcar- Bluishbamoyl)-benzoyla.mino]-anthraquinone. red.

380 1,4-di-[4-(3-sulphamoy1-phenylcarbamoyl)-ben- Red.

zoylaminol-anthraqmnone.

381- 1,4-di-[4-(4-cs rbamoyl-phenylearbamoyl)-ben- Blnish zoylamlno-antl1l'aqulnone. red.

382.-. 5,8-dichloro- ,4-di-[4-(n-butylearbamoy])-ben- Red.

zoylamino -anthraquinone.

383.-- 1,5-(4-pheny'carbamoyl-benzoylamlno)-anthra- Yellow.

qumone.

384- 1,5-di-[4-(4-su1phamoyl-phenylcarbamoyl)-ben- Do.

zoylaminol-anthraquinone.

385- 1,5di-[4-(4-carbamoyl-phenylcarbamoyl)-bon- D0.

zoylaminol-anthraquinone.

386-.. 1,5'di-[4-(2,5-dichloro-phenylcarbamoyl)-ben- Do.

zoylaminol-anthraquinone.

387- 1,5-dihydroxy-4,8-di-[4-(2,5-diehloropheny1ear- Blue.

bamoyD-benzoylamlnol-anthraquinone.

388. 1,5-dihydroxy-4,8-d1-[4-(4-methoxy-phenylcar- Do.

bamoyl)-benzoylam1n01-anthraquinone.

389. 1,5-dihydr0xy-4,8-di-[4-(4-metl1yl-phenylcaIbamoyD- Do.

benzoylaminol-anthraquinone.

390- 1,5'dihydroxy-Z-(4-methoxy-phenyl)4,8-(11-(4- D0.

butylcarbamoyl-benzoylamino)-anthra.quinone.

phenylcarbamoyl-benzoylamino)-anthraqulnone.

EXAMPLES 392-404 Printing pastes prepared according to Example 13, but45 using corresponding amounts of the dyestuffs stated in the Table,yield fast offset prints in the specified shades.

Ex. Dyestufi Shade 392-. 1, 5-dlhydroxy-4,8-di-(Smethylcarbamoylnaphthoyl- Blue.

(1)-am1no)-anthraquinone.

393.. 1, 5-dihydroxy-4, 8-di-[4-(5-chloro-2-cyanophenylcar- Do.

bamoyl)-benz0ylaminol-anthraquinone.

394.- 1, 5-dihydroxy-4, 8-di-[4-(2, 4-dicyano-pheny1carbam- Do.

oyl)-beuzoylaminol-anthraquinone.

395.- 1, 5dlhydroxy-4, 8-di-t4-[2-chloro-5-(2-hydroxyethyl- D0.

sulphamoyl)-phenylearbamoyll-benzoylamino)- anthraquinone.

396.- 1, 54flhydroxy-4, 8-d1-[4-(6-carbamoylnaphthy1-(2)- Do.

earbamoyD-benzoylamino]anthraquinone.

397... 1, 5-dihydroxy-4, 8-di-[4-(2-carbamo l-4-sulphamoyl- Do.phenylcarbamoyl)-benzoylamino enthraquinone.

398-- 1, 5-dihydroxy-4, 8 di-I-(4-phenylazophenylcarbam- Do.

oyl)-benzoylamlnol-anthraquinone.

399.. 1, 5dlhydr0xy-4, 8-di-(4-pyrldy1-(2)-ea.rbamoyl-ben- Do.

zoylamino)-anthraquinone.

400.- 1, 5-dihydroxy-4, 8-di-l4-('y-pieolylcarbam0yl)-benzoyl- Do.

amino]-anthraquinone.

401.- 1, 5-dihydroxy-4, 8-di-[4-(Z-phenyl-benzotriazolyl-(5)- Do.

carbamoyl)-benzoylaminol-anthraquinone.

402-..- 1, 5-dihydroxy 8-di-(4-thiazo1y1-(2)-carbamoy1- Do.

benzoylamino -anthraqninone.

403-. 1, 5-dihydroxy-4, 8-dl-[4-(6-methoxy-benzothiazolyl- D0.

(2)-carbam0yl)-benzoylamin0]-anthraquin0ne.

404.- 1, 5-dihydroxy-4, 8-di-[4-(2-meth y1-benz0thiazo1y1-(6)- Do.

carbamoyl)-benzoyhminol-anthraquinone.

What is claimed is:

1. The dyestuff: 4 (4-chloro-benzoylamino)-1-[4-(2-chloro-phenylcarbamoyl)-benzoylamino]-anthraquinone.

2. The dyestuff: 4 (4-chloro-benzoylamino)-1-[4-(4- sulphamoylphenylcarbamoyl)-benz0ylamin0] anthraquinone.

References Cited UNITED STATES PATENTS 3,598,831 8/1971 Pfister 260-3773,436,401 4/ 1969 Pfister 260-377 3,361,765 1/1968 Weber 260-377 FOREIGNPATENTS 1,098,130 1/ 1968 Great Britain 260-377 1487045 5/ 1967 France260-377 LORRAINE A. WEINBERGER, Primary Examiner E. J. SKELLY, AssistantExaminer US. Cl. X.R.

106-23, 164, 193 P; 162-134; 260-37 P, 37 N, 39 P, 40R, 4OTN, 41 C, 41.5R, 143, 192, 207.1, 256.4 Q, 256.5 R, 272, 303, 308 R, 316, 327 R, 327TH, 329.2,

